Alkylation of hydrocarbons



Feb. 5, 1946. 1 A. CLARKE LKYLATION OF HYDOCARBONS Filed Maren 19, 1940 Patented Feb. s, `1946 UNITED STATE s PATENT yoFF-1ct:

ALKYLArIoN oF mmnocAltnoNs y Louis A. Clarke, Fishkill, N; Y., assigner, by mesne Y assignments, to The Texas Company, New York, N. Y., acorporationot Delaware ApplicationMarch 19,1940, Serial No. 324,784

'zv claims. (ci. aso-,6834

nisinvenuen relates te the amyledcn f iso- Vparaflln hydrocarbonswith oleiin hydrocarbons'in the presence o f an alkyiation catalyst comprisinga metallic halide and has particular application to the manufacture of high anti-knock ga'soline'hydrocarbons suitable for use 'in the production of Broadly the invention contemplates a continuous process of alkylation wherein the feed hydro,-

carbons are subjected to reaction in a reaction zone or in a plurality of reaction zones containing the solid catalyst in divided or pulverulent form and in which zone or zones the solid catalyst is continuously subjected to washing during the reaction-so as to'maintain it in an active form.'

ticles of aluminum chloride rapidly become coated l during the reaction with a gummy fluid complex of aluminum chloride and hydrocarbons so thatthe catalyst is soon rendered substantially ineilective.

In accordance with the present invention the catalyst is subjectedlto continuous washing with liquid hydrocarbons in situ and during the reaction so as to remove the undesired complex material substantially as' rapidly as formed. Moreover, the

process is eiected at somewhat higher tempera-- tures than disclosed, for example, in the abovelacted hydrocarbons, are removed from the top offrom top to Abottomiotthe reaction tower, while gaseous iTow is from-bottomto top.

Gaseous materials, including inert and unrethe tower and the reacted hydrocarbons, including gasoline hydrocarbons, are accumulated in the bottom of the tower together with the complex metallic halide-hydrocarbon compounds washed from the solid catalyst during the reaction.

'I'he isoparanin hydrocarbon is introduced to the .I reaction tower substantially in excess of that required for reaction with the olefin hydrocarbons in the feed and provision is made for recycling a substantial proportion of liquid hydrocarbons, includl ing isoiriarailln. Excess isoparailin and alkylated hydrocarbons are separated from the reaction mixture accumulating in the bottom of the tower and lreturned-in substantial amount'to the top of the tower so as to provide a reflux in sutllcient s I quantity to continuously wash the solid lcatalyst supported within the tower.

mentioned patent. It hasbeen found that while v the reaction between ethylene and isobutane proceeds very slowly at around F.' or lower, the

reaction is much more rapid at a temperature -oi around or 120 F. or in the vrange 110' F. to F. y 4

In carrying out the continuous process of this invention one or more reaction vessels packed with the solid catalyst in lump or granularv form are employed. ,The gaseous oleiln hydrocarbons are A introducedto the lower portion of the reaction vessel. while' the isoparailln is advantageously introduced to the upper portion thereof.v The operation isthus conducted so that there is liquid Bow u relatively deep The eomplexmeteme halide-hydrocarbon enm-A pounds segregated from the reaction mixture a're v continuously discharged from the system.

Advantageously the reaction is `eiected in the, presence of a small amount of a promoter substance, such as propylene or butylene, etc. That portion of the 'reaction mixture separated from the complex compounds and not recycledfis drawn of! and further processed to recover the alkylated hydrocarbons. However, where a plurality of reaction towers or zones are. employed. all or a portion of this non-recycled mixture may be 4passed to the succeeding zone so that any unreacted oleiln' hydrocarbons present may be again subjected to contact with an additional quantity of isoparailin hydrocarbons. Gaseous oleiln feed may be introduced to the succeeding reaction zone` along with. Vor in addition to, themixture entering such s ucceeding zone from thepreceding zone.

In'order to explain the process more Acompletely reference will now be made to the accompanying drawing illustrating, by means of a flow diagram, one method of carrying out the process:

As indicated in the drawing, a gaseous hydrocarbonfeed, comprising mainly ethylene, is conducted vfrom a source not shown through a pipe I and branch pipe v2 to the lower portion of a reaction tower 3.

The reaction tower is packed with aluminum v chloride in lump or 'granular form. yThe catalyst may be supported within the tower in any suitable manner. Thus, it maybe in the form of a single bed or in the form o! a plurality of rela-tively shallow beds. depending upon the height of the tower. As indicated in the drawing, however, a single bed of catalyst is provided, since this facilitates the addition of fresh catalyst to the tower during the operation of the process from a hopper device 4. In this way a bed of uniform depth may be maintained continuously during the operation of the process.

A hydrocarbon fraction containing mainly isoparaflin hydrocarbons, such as isobutane, is conducted from a source not shown through a pipe 5 and introduced to the upper portion of the tower 3.' The isoparafn hydrocarbon is intro` duced substantially in excess of that required for reaction with the olefin and may, for example,

be introduced so as to provide a molal ratio of five parts of isoparafiln to one part of ethylene.

A temperature of around 100 to 130 YF. is maintained within the tower. The temperature may be maintained in this range by passing a cooling medium through a jacket surrounding the reaction tower or through coils supported within the contact mass. The necessary cooling may also be provided by adjusting the temperature of the isoparaffin hydrocarbon feed, a part of which feed may be introduced at ldifferent levels within the tower.

of hydrogen chloride may be introduced from a e pipe 2l with the feed hydrocarbons to the reaction tower 3; also, it is advantageous to promote the reaction by eecting it in the presence of a small amount of more reactive and higher molecular weight olefin hydrocarbons, such as propylene and butylene. The -amount of propylene -added as a promoter may be in the range of around 1 to less than 20% by weight of the olefin present in the feed.

lThe portion of alkylated hydrocarbons and isoparaiiin hydrocarbons not recycled through the pipe 1 is passed through a pipe I0 leading to the upper portion of a reaction tower I2, sim` liar to the reaction tower 3. Fresh olefin feed conducted from pipe l and branch pipe I3 is introduced to the lower portion of the reaction tower I2, together with gaseous constituents from pipe Ilcommunicating with pipe 8 previously referred to.

The operation of the reaction tower I2 is sim- I liar to that described for the reaction tower 3,

A pressure of around 125 to 200 pounds may be maintained within the tower, or a pressure sumcient to maintain at least a substantial portion of the isoparaflln feed in the liquid phase within the tower.

Under these conditions, reaction between the' olen and isoparailln feed hydrocarbons results in forming alkylated hydrocarbons comprising gasoline hydrocarbons,

The alkylated hydrocarbons, includingunreacted isobutane, flow downwardly through the tower and'accumulate in the bottom thereof,

i from which they are withdrawn througha pipe 6 and by means of a pump.

A portion of the withdrawn -mixture'lis returned through a pipe 1 to the top of the tower and in,

troduced thereto at a point above the contact mass, thus providing a reflux of wash liquid.

This wash liquid flows back down through the contact mass and washes from the solid catalyst particles the complex aluminum chloride-hydrocarbon 'compounds formed during the reaction and adhering to the solid catalyst. The wash liquid and removed complex compounds also ac-V cumulate in the bottom of the tower.

Advantageously, sufficient settling space is provided in the bottom of the tower in which to effect phase comprising the. undesired complex compounds and aluminum chloride sludge, while the upper phase comprises v'alkylated hydrocarbons and isoparaln hydrocarbons.'

-The complex vmaterial is-dischar'ged from the system through a piped.'

If desired, this phase separation may be effected in a separate settling vessel located outside the tower. i v

Gaseousmaterial accumulating .in the top of -in the bottomof the reaction tower I 2 are drawn through a pipe Il for discharge from'the system. The gaseous materials, including methane, ethane, hydrogen, etc., accumulating in the top of the tower I2, are withdrawn through a pipe I8 and passed toI ahfractionator I-Q wherein the hydrocarbons, comprising isobutane and'higherv 'boiling liquid, may be recovered for further dis' position, as, for example, recycling through the system. While two reaction towers have been described, it islcontemplated that any number of towers may be employed. If desired, a single relatively tall towermay be used. y In accordance with the invention, in reacting ethylene with isobutane in the presence of aluminum chloride, a product isobtained which'boils boiling around 136 F., which has an octane ratsettling and separation into phases, the lower ing of 95 C. F. R. M.

While aluminum chloride has been mentioned specifically, nevertheless, it is contemplated that other metallic halides, such as aluminum bromide and zirconium chloride, may be employed.

The alkylation of a gaseous olefin fraction,- consisting essentially of ethylene, has been specically described above.l However, it is contemplated that the process maybe applied to the the tower, such as methane,'ethane and hvdrodischarge from the system. However, in the 'cai-bons they may be passed to the next succeeding stage, as will be described, or maybe recycled gen, is withdrawn through a pipe 9 for ultimate through pipe 20 to the bottom of the tower, ref' entering the tower' with the fresh feed. In order to activate the catalyst a small amount alkylation of other olens, including ,Cs olefin. Also, higher molecular weight isoparaiiln hydrocarbons, besides isobutane, may be used.

fbbviously manymodications and variations of the invention, as hereinbefore set forth, may be made lwithout departing from the spirit and scope thereof, and therefore only such limitations should be imposedas are indicated in the' `appended claims.

I claim: i

1.- In a continuous process for alkylat'ing normally gaseous oleilns with isoparailin hydrocarbons by contact with an alkylation catalyst comprising u an `active metallic halide in solid particle form, the steps comprising maintaining a reaction tower packed with the solid metallic halide particles, introducing the olefin feed to the lower portion of said tower, introducing the isoparafiin feed to the upper portion thereof substantially in excess of that required for reaction with the. oleilns, maintaining the tower at a escasas temperature suillcientoto effect the alkylation reaction, maintaining a the tower under pressure suillcient to` maintain at least a substantial portion of the isopanaiiln feed in the liquid phase,

wherebyisoparailln is alkylated by the olen to produce gasoline hydrocarbons of high antiknock value while the solid particles of the catalystbed tend to become coated with metallic halide-hydrocarbon complex removing gaseous material, including inert and unreacted hydrocarbons, from 'the topof said tower, accumulat- '20 ing from the lower portion of said tower liquid hydrocarbons including excess isoparamn and within the tower.

' 2. In the alkylation of a low-boiling isoparafiin with a normally gaseous olefin in the presence of a metallic halide alkylation catalyst for the production of gasoline hydrocarbons of high anti-knock value, the method which comprises maintaining aiixed bed consisting essentially of solid parti/cles of active metallic halide alkylation catalyst in ,a reaction zone,l continuously passing the isoparain and the normally gaseous olen withi the isoparaiiln in molar excess of the olefin through said bed under conditions such that isoparaifin is alkylated by the olefin to produce gasoline hydrocarbons of high anti-knock reaction zone, and recycling at leasta portion of value, while the solid particles of the catalyst bed tend to become coated with metallic halidenydrocarbon complex, simultaneously passing through said bed a substantial proportion of previously formed liquid hydrocarbon reaction prod.

fucts of said alkylation reaction to continuously wash the coating of metallic halide-hydrocarbon complex from the particles of said fixed catalyst bed, removing from said reaction zone liquid hydrocarbon reaction products togetherl with metallic halide-hydrocarbon complex washed from said fixed bed of active metallic halidel particles, separating the liquid hydrocarbon reaction products from said complex thus removed from the fixed bed, dividing said separated liquid hydrocarbon reaction products and diverting one portion thereof` to fractionation for the recovery of alkylate therefrom, and directly recycling another portion of said separated liquid hydrocarbon reaction products to said reaction zone to serve as the above mentioned washing liquid for the fixed catalyst bed, whereby the metallic halide-hydrocarbon complex coating is continuously removed from the metallic halide particles to maintain high activity of said fixed metallic halide catalyst bed over substantial periods of continuous operation. v

3. The method in accordance with claim 2, wherein the isoparailln is introduced in liquid phase and the oleiin is introduced in'gas into said reaction zone. and the liquid isoparamn and gaseous olefin now countercurrently to each other through said bed. K u

' 4. The method in accordance with claim 2, wherein an elongated vertical reaction zone containing the confined catalyst bed is provided, isoparamn is introduced in liquid phase adjacent the upper end4 of said reaction zone and olen yis introduced in gas phase adjacent the lower end of said reaction zone, the liquid isoparaflln and the gaseous olen flowing countercurrently'to each other through said bed, and the said recycled liquid hydrocarbon reaction products are introduced into said reaction zone adjacent the upper end of said `tied and flow downwardly therethrough. p f

'5. The method oi continuously alkylating a low-boiling isoparaifln with a normally gaseous olefin ofV lower molecular weight than the said isoparafiln in thepresence of an active metallic halide alkylation catalyst, which comprises continuously feeding thenormally gaseous olefin in gas phase and the low-boiling isoparaln in liquidv phase, with the isoparafiin in'substantial molar excess of the olen, into a reaction zone and 'passing the same in contactwith each other through a maintained and relatively fixed body of the metallic halide catalyst under alkylating conditions, whereby isoparaln is -alkylated by theolen to produce a normally liquid alkylate comprising gasoline hydrocarbons of high antiknock value, continuously removing a liquid stream of reaction products comprising alkylate and excess isoparafiln substantially free from olen from the reaction zone and recovering alkvlate therefrom, separately removing a gase- A ous stream comprising unreacted olefin from the said gaseous stream'in ,gas phase' to said olein feed for return tothe reaction zone.

6. The method of continuously alkylating a low boiling isoparafiln with a normally gaseous oleiin in the presence of an aluminum chloride alkylation catalyst, which comprises continuously feeding the oleiin in gaseous phase and the isoparaffin, with the isoparafn in substantial molar excess of the oleiln, into a reaction zone containing a maintained and relativelyxed body of the aluminum chloride alkylation catalyst, providing a pressure within said reaction zone to maintain lat least a substantial portion of the low boiling ditions, whereby isoparafiln is alkylated with the olefin to produce an alkylate comprising Agasoline hydrocarbons of high anti-knock value, continuously withdrawing a 'stream of reaction products from said 4reaction zone and recovering alkylateA therefrom.

7. The method of continuously alkylating a low boiling i'soparailln with a nbrmally gaseous olenn of lower molecular weight than the said isoparafiln in the presence of an active metallic halide alkylation catalyst, which comprises continuously passing the normally gaseous olen in gas phase and the low boiling isoparaflin in liquid phase, with the isoparailln in substantial molar excess of the olen, in contact with each other through Aa maintained and relatively fixed body of the metallic hande catalyst in an alkylation reaction zone under alkylating conditions, whereby -isoparafln is alkylated by the olefin to produce a normallyv liquid alkylate comprising gasoline hydrocarbons of high anti-knock value, and wherein a gaseous hydrocarbon phase containing un` reacted olen and Ya. liquid'hydrocarbon phase comprising alkylate and excess isoparafn continuously separate from the maintained body of catalyst in said reaction zone, continuously withdrawing a. stream o! said liquid hydrocarbon phase, recycling a portion of said withdrawn liqv uid hydrocarbon stream comprising alkylate and 2,394,368 excess iscparalnto the said reaction4 zone for" catalyst body.

LOUIS A. CLARKE. 

